Lakes and the production thereof



Unite LAKES AND THE PRODUCTION THEREOF Emil Stocker, Riehen, near Basel, Switzerland, assignor to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm No Drawing. Application January 27, 1956, Serial No. 561,941

The present invention concerns lakes which are distinguished by their remarkable fastness to light and slight tates Patent migratory powers in organic binding agents or synthetic materials. It also concerns processes for the production of the new lakes, in addition processes for the production of high molecular natural and synthetic substances in the form of lacquers and plastic masses coloured fast to light with the new lakes.

It has been found that remarkably fast to light, practically non-migrating lakes are obtained if a diazotised aminobenzene sulphonic acid containing at least two acid dissociating water solubilising groups is coupled by methods known per se with an o-hydroxyaryl carboxylic acid arylamide coupling in the o-position to the hydroxyl group and the monoazo dyestuff obtained is laked by methods known per se with compounds of polyvalent metals.

The aminobenzene sulphonic acids used according to the present invention can contain, as further acid dissociating water solubilising groups, sulphonic acid and carboxyl groups and in addition, further substituents usual in azo dyestuffs, e. g. halogen, alkyl or alkoxy groups. The use of such aminobenzene sulphonic acids as diazo components which contain a carboxyl or a sulphonic acid group in the neighbouring position to the amino group is particularly advantageous.

The diazotisation can be performed as is usual with sodium nitrite in a mineral acid medium in the cold according to the direct or indirect method.

Of the coupling components used according to the present invention, the o-hydroxyaryl carboxylic acid arylamides coupling in the o-position to the hydroxyl group, preferably the 2.3 -hydroxynaphthoic acid arylamides which are derived from primary amines of the benzene and naphthalene series are used. They can contain the.

further substituents usual in azo dyestuffs in the arylamide radical, e. g. halogen, alkyl and alkoxy groups. Possibly, also 2-hydroxycarbazole-3-carboxylic acid arylamides or 3-hydroxycarbazole 2 carboxylic acid arylamides, further 3-hydroxydiphenylene oxide-2-carboxylic acid arylamides can be used. The coupling is performed in an alkaline medium or, when the azo components are finely distributed, also in weakly acid suspension in the presence of alkali metal salts of low fatty acids-which buffer the mineral acid. On completion of the coupling, the dyestulf is either isolated and dissolved in fresh water or the coupling solution is neutralised, possibly warmed and then the soluble salts of polyvalent metals are added evenly to the dyestuif solution; advantageous are solutions of earth alkali or earth metals, possibly also solutions of manganese, iron, zirconium or tin salts. The lake is precipitated advantageously at temperatures of 80 to 100 C. Aqueous solutions of calcium chloride, strontium chloride or nitrate, barium chloride, aluminium sulphate, manganous chloride or manganous sulphate are examples of precipitating agents. The precipitating agents are used in such amounts that there is one 'dyestuff moleno ICC cule to at least one polyvalent metal atom. It is of advantage, however, to use an excess of precipitating agent.

To attain lakes of a soft texture it is often advanta geous if the monoazo dyestufis are laked with metal salts in the presence of capillary active dispersing agents and/or of other protective substances which on drying, prevent the formation of a hard core. For this purpose, for example, solutions of alkali soaps of higher fatty acids, colophony soaps or also emulsions of fats, waxes, paraffines, fatty oils or of the plasticisers usual in the lacquer and plastics industry which are produced with the aid of soap or other emulgators, are suitable. It is also possible to perform the laking in the presence of substrate, e. g. in the presence of aluminium hydroxide, barium sulphate or titanium dioxide. Also mixed precipitates can be obtained with two or more different metal was.

The precipitated lakes are then either isolated, dried and converted by milling into a form which is economical in use or they are further worked up as wet pastes, e. g. dispersed according to the flushing process in organic binding agents or plasticisers.

According to the method sketched above, vivid red to brown red lakes are obtained with the new dyestuflfs which are distinguished by remarkable fastness to light and stability to heat. Due to these properties they are very suitable for pigmenting higher molecular natural and synthetic substances, for example in the form of lacquers or plastic masses and in particular for the dyeing of so-called stoving lacquers. Because of their slight tendency to migrate, they are very valuable in these substances.

The following examples serve to illustrate more clearly the subject matterof the invention without limiting it in any way. Where not otherwise stated, parts are given as parts by weight and the temperatures are in degrees centigrade. Where parts by volume are expressly mentioned, their relationship to parts by weight is as that of litres to kilogrammes.

Example 1 25.3 parts of aniline-2.5-disulphonic acid in the form of the monosodium salt are dissolved in 480 parts of water, cooled to 0 to 3 and, after the addition of 15 parts by volume of 10 N-hydrochloric acid, diazotised with 20.7 parts of sodium nitrite solution 33.3%.

Also 32.3 parts of B-hydroxynaphthoic acid-l-naphthylamide are dissolved with the aid of 66.5 parts of caustic soda lye 30% and 7 parts of Turkey red oil in 1800 parts of water at -95 After the addition of a little decolourising carbon, the solution is filtered and the filtrate is brought up to 3000 parts by volume and to a temperature of 18-20".

A cold solution of 27 parts of 80% acetic acid in parts of water are added to the diazo solution and the mixture is quickly added while stirring to the solution of the coupling components. On completion of the coupling, the reaction is made neutral to litmus paper with sodium carbonate and the laking is performed as follows:

200 parts of a 2% linseed oil emulsion are added and 24 parts of calcium chloride dissolved in parts of water are added dropwise within 15 minutes. The temperature is then raised to 75-80, kept there for one hour and then the mixture is allowed to cool overnight. It is filtered, the precipitate is washed and dried at 70.

The red lake is suitable, for example for thecolouring of polyvinyl chloride in the mass where it is distinguished by a beautiful nuance, high fastness to lightand stability to heat and migration. Also on more slightly pigmenting the fastness to light is still astoundingly good.

If in this example the calciumchlo'ride is replaced by equivalent amounts of strontium chloride, manganous chloride, aluminium sulphate, iron (III) ;chloride,tin (lI) 8619. parts of fi hydroxynaph'thoic acid ZM dimethoxy S- chloranilide are dissolveid with' the aid-of 250 i parts by .volume of 2 N-caustic soda lye and*7;=parts-of Turkey-red oil-indfiOOparts of-water at 90- 95. :After the addition ofdecolour ising carbon; the solution-is =filtered-and the filtrate is brbught up toii'OOO parts by volume-audio a temperature of '3 840 1'80 parts by -volume of 2 bl-acetic ac'id. are addedto the:diazosolution,- the mixtureds quickly adde'd while stir" ring I to the naphtholate solution and, on completion of the coupling =-'the 'reaction -is --made-'neutral with sodium carbonate solution 'tolitmus paper.

'The couplingmixture is 'then-heatedto 85=-90,a-solution of 40 parts of colophony soap in 1600 parts of water of 85 is added and laking is performed in minutes by the addition dropwise of 60 parts of bariumchloride dissolved in 250 parts of water. After another two hours, the-mixture is allowed to cool, stirred -overnight,"filtered and the precipitate is washed'anddried at 60.

The lake produces somewhat morebluish red shades and has similar propertiesto those describedinExample 1.

The sodium salt of the dyestuff can also be'reacted with the equivalent amounts of strontium nitrate, manganous chloride, aluminium chloride, iron (III) chloride,'tin (II) chloride, tin (IV) chloride, orzirconium oxychloride instead of with barium chloride. Red to brown red lakes are obtained which can be used for example 'to pigment lacquers.

Example 3 A diazo solution is prepared according to the information. given in Example 1. Also 32.1 parts of fl-hydroxynaphthoic acid-2-methyl-4-chloranilideare dissolved with the aid of 66.5partsof caustic soda lye 30%:and 7 parts of Turkey red oil in 1800 parts of water at 90-95. The solution is brought to 2100 partsby volume and to a temperature of 36-38, 50 parts'by volume of 2 N-sodium carbonate solution-and, while stirring,.20 partsof sodium bicarbonate are added and the clarified.diazosolutionis poured'in within 30 minutes. When the'coupling is complete, the solution is made neutral tolitmus paper with acetic acid, heated:to 85.90, asolutiomof parts-of colophony soap in 1200 parts of water of 85 is addedand, Within 15.1ninutes, 42 partsofsbarium chloride-dissolved in 175 parts of .waterare added. Afterheatingfor 2 hours.at'85+90, :the mixture is allowed to cool overnight, filtered, the filter residue is washed and dried at 60.

Thedakeis suitable, for example, for the production of brilliant red transparent stoving lacquers producedprincipally from.ureadormaldehydealkydresins and is distinguished by very good fastness to light and-cross lacquer-lug.

.Example 4 25.3 parts of aniline-2.4-disulphonic acid in the form of its disodium salt are dissolved in 400 parts of water, 25 parts by volume of 10 N-hydrochloric acid'are added and the solution is diazotised at 0-3 with 100 partsby volume of 1 N-nitrite solution.

Also'32.3 parts of p-hydroxynaphthoic acid-l-naphthylamideare dissolved with the aid of67 parts of caustic soda lye and 6.7 partsof Turkey red oil in 1800 parts of waterat 95 The 'solutionis filtered,,the volumeis made upto'2000parts'and-it is heated to'30T32" and 20 parts 01? sodium bicarbonatedissolved in- 200,parts of water are quickly added while-stirring. Immediately after'the addition of the sodium bicarbonate, the clarified .diazo solution is poured'inwithin-15=minutes. Whenthe couplingis complete,- the reaction is made 'neutraltoilitmus paper -with lfl N-hydrochlorie acid.

Afterheating to 85-90, a solution of 25 parts of colophony soap in 1200 parts of water of is added and the product is precipitated in 15 minutes with 42 parts of barium chloride dissolved in 175 parts of water. The whole is heated for another hour at -90", allowed to cool overnight, the product is filtered ofi, washed a little and dried. at 60.

Brilliant red, transparent stoving lacquers can be produced-with this precipitationproduct which have good fastness to light and cross lacquering.

Example 5 -oxy 5-chloranilide are dissolved in 1800 parts of water at ---95with theaddition of66.5 parts of 30% caustic soda lye and 7 parts of Turkey red oil. After the addition of a little decolourising carbon,-it is filtered and the volumeis brought up to 30%-parts and the'temperature 180 parts by volume of 2 N-acetic acid at'5" are added to'the diazo'solution whereupon themixture is quickly addedwhile stirring to the naphtholate solution.

On completion of the coupling, the reaction is made neutral to litmus paper with sodium carbonate solution, 200 parts of-a 2% emulsion of a vegetable oil are added and then 54 parts of barium chloride dissolved in'220 parts of water are added and the whole is heated for one hour at 75-80. After cooling overnight, the product is filtered off, washed a little and dried.

The product can'beused for the production of red stoving lacquers which-have verygood fastness tolight and cross'lacquering.

If in the above example, instead of 36.9 parts of hydroxynaphthoic acid-2.4-dimethoxy-5-chloranilide, 32.3 parts of ,B-hydroxynaphthoic acid-I-naphthylamide are used and otherwise the same procedure is followed, then a lake with a somewhat more yellow shade is obtained.

Example 6 A diazo solution 'is prepared, .analogous to that in Example 1, from 21.7 partsof Z-amino-A-sulphobenzoic aci Also36i9 parts ,of fi-hydroxynaphthoic acid-2.4-dimethoxy-S-chloranilide are dissolved analogous to the method described in Example. 1, and the coupling and laking is performed asigiven in that example. A red lake isobtained which, in polyvinyl chloride containing ,plasticisers,:has good fastness to light and only a very slight tendencytto bleeding.

Example 7 '2 -amino-5.sulphobenzoic acid diazotised, coupled with fl-hydroxynaphthoic acid anilide and hiking with calcium :chloride as described in Example 1, produces a lake which in transparentstoving lacquers is brilliant orange-red and has very good fastness to light and cross lacquering.

Example 8 The barium lake of the dyestuflf from j2-amino-5- sulphobenzoic acid and fl-hyclroxynaphthoic 'acid-lnaphthylamide produced according to Example 1 is :brilliant red in transparent stovinglacquers and has very good fastness to light and cross lacquering.

Example 9 25.15 parts. of. Z-chloro 5 amino-4-sulphobenzoic acid are drssulvedinZOO parts of water with thesaidot parts ,by volumev of 2 N-sodium. carbonate. solution; .100 parts of 1N sodiumv nitrite are then. added. and, at ,0-3 7, 280 parts by'volume of 1 N-hydrochlon'c acid are added While stirring within one hour, the temperature being kept at 03.

Also 32.1 parts of B-hydroxynaphthoic acid-2-methyl- 4-ch'l0ranilide are dissolved in 1800 parts of water at 95 with the addition of 6 parts of Turkey red oil and 66.5 parts of 30% caustic soda lye. A little decolourising carbon is added, the mixture is filtered and the filtrate is brought up to 2000 parts by volume and to a temperature of 0-3". After the addition of 20 parts of sodium bicarbonate (as saturated solution), the diazo suspension is poured in within 10 minutes.

When the coupling is complete, the coupling mixture is neutralised with acetic acid, heated to 85-90, 300 parts of 2% vegetable oil emulsion are added; a solution of 24 parts of calcium chloride in 160 parts of water is added within minutes and the whole is heated for another 2 hours at 8590. After cooling overnight, the product is filtered off, washed a little and dried at 60. In transparent stoving lacquers, the lake has a brilliant yellowish red shade and is fast to cross lacquering. It has good fastness to light.

If in the above example, 32.3 parts of fl-hydroxynaphthoic acid-l-naphthylamide are used instead of 32.1 parts of B-hydroxynap-hthoic acid-2-methyl-4-chloranilide and otherwise the same procedure is followed, then a lake having a similar nuance is obtained.

Example 10 67 parts of polyvinyl chloride, 33 parts of d-ioctyl phthalate 2 parts of di-butyl tin dilaurate and 0.65 part of the red lake according to Example 1 are homogeneously worked up on a set of hot mixing rollers. The mixture is then drawn out into a foil of the desired thickness.

Example 11 formula N=N- )xQ X2 R wherein one of X1 and X2 is SOsH and the other is selected from the group consisting of SO H and COOH, R is a member selected from the group consisting of H,

CH3 and Cl, B represents an aromatic radical containing at least one six-membered carbocyclic nucleus and at most two such nuclei condensed with one another, with a polyvalent metal selected from the group consisting of calcium, strontium, barium, aluminium, zirconium, tin and manganese.

2. The calcium lake of the azo compound having the formula:

SOsH OH O O-NH SOsH 4. The barium lake of the azo compound having the formula:

5. The calcium lake of the azo compound having the formula:

OCH:

00011 OH OO-NHOOOH3 SOaH '6. The barium lake of the azo compound having the formula:

COOH

SOaH

References Cited in the file of this patent UNITED STATES PATENTS Wagner Mar. 13, 1934 Zerweck et al. Feb. 9, 1937 OTHER REFERENCES 

1. THE LAKE OF A MONOAZO COMPOUND HAVING THE FORMULA: WHEREIN ONE OF X1 AND X2 IS SO3H AND THE OTHER IS SELECTED FROM THE GROUP CONSISTING OF SO3H AND COOH, R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF H, CH3 AND CL, B REPRESENTS AN AROMATIC RADICAL CONTAINING AT LEAST ONE SIX-MEMBERED CARBOCYCLIC NUCLEUS AND AT MOST TWO SUCH NUCLEI CONDENSED WITH ONE ANOTHER, WITH A POLYVALENT METAL SELECTED FROM THE GROUP CONSISTING OF CALCIUM, STRONTIUM, BARIUM, ALUMINIUM, ZIRCONIUM, TIN AND MANGANESE. 